NKN [(Na,K)NbO3] is a candidate lead-free piezoelectric material to replace PZT [Pb(Zr,Ti)O3]. A single crystal has excellent piezoelectric-properties and its properties are dependent of the crystal orientation direction. However, it is hard to fabricate a single crystal with stoichiometrically stable composition due to volatilization of sodium during the growth process. To solve this problem, a solid solution composition is designed (Na,K)NbO3-Ba(Cu,Nb)O3 and solid state grain growth is studied for a sizable single crystal. Ceramic powders of (Na,K)NbO3-M(Cu,Nb)O3 (M = Ca, Sr, Ba) are synthesized and grain growth behavior is investigated for different temperatures and times. Average normal grain sizes of individual specimens, which are heat-treated at 1,125 oC for 10 h, are 6.9, 2.8, and 1.6 m for M = Ca, Sr, and Ba, respectively. Depending on M, the distortion of NKN structure can be altered. XRD results show that (NKN-CaCuN: shrunken orthorhombic; NKN-SrCuN: orthorhombic; NKN-BaCuN: cubic). For the sample heat-treated at 1,125 oC for 10 h, the maximum grain sizes of individual specimens are measured as 40, 5, and 4,000 m for M = Ca, Sr, and Ba, respectively. This abnormal grain size is related to the partial melting temperature (NKN-CaCuN: 960 oC; NKN-SrCuN: 971 oC; NKN-BaCuN: 945 oC).

This work focuses on the electrical conduction mechanism in a lead free (Na0.5K0.5NbO3 ; NKN) ceramics system with LiNbO3 content of approximately critical concentration x ≥ 0.2. Lead free (1-x)(Na0.5K0.5)NbO3 - x(LiNbO3), NKN-LNx (x = 0.1, 0.2) ceramics were synthesized by solid-state reaction method. Crystal structures are confirmed by X-ray diffraction. The electric-mechanical bond coefficient k p decreases and the phase transition temperature T c increases with increasing x content, as determined by dielectric and piezoelectric measurements. The value of the real dielectric constants ε' and kBTε'' showed anomalies around T c (462 oC in the NKN-LN0.1 and 500 oC in the NKN-LN0.2). For the ionic conduction of mobile ions, the activation energies are obtained as EI = 1.76 eV (NKN-LN0.1) and EI = 1.55 eV (NKN-LN0.2), above T c, and EII = 0.78 (NKNLN0.1) and EII = 0.81 (NKN-LN0.2) below T c. It is believed that the conduction mechanisms of NKN-LNx ceramics are related to ionic hopping conduction, which may arise mainly due to the jumping of Li+ ions.

New lead-free piezoelectric ceramics 0.96[{Bi0.5 (Na0.84 K0.16)0.5}1-xLax(Ti1-y Nby)O3]-0.04SrTiO3 (BNKT-ST-LN, where x = y = 0.00 ≤ (x = y) ≤ 0.015) were synthesized using the conventional solid-state reaction method. Their crystal structure, microstructure, and electrical properties were investigated as a function of the La and Nb (LN) content. The X-ray diffraction patterns revealed the formation of a single-phase perovskite structure for all the LN-modified BNKT-ST ceramics in this study. The temperature dependence of the dielectric curves showed that the maximum dielectric constant temperature (Tm) shifted towards lower temperatures and the curves became more diffuse with an increasing LN content. At the optimum composition (LN 0.005), a maximum value of remnant polarization (33 C/cm2) with a relatively low coercive field (22 kV/cm) and high piezoelectric constant (215 pC/N) was observed. These results indicate that the LN co-modified BNKT-ST ceramic system is a promising candidate for lead-free piezoelectric materials.

Studies on lead-free piezoelectrics have been attractive as means of meeting environmental requirements. We synthesized lead-free piezoelectric (Bi1/2Na1/2)TiO3-Ba(Cu1/3Nb2/3)O3 (BNT-BCN) ceramics, and their dielectric, piezoelectric, and strain behavior were characterized. As BCN with a tetragonal phase was incorporated into the rhombohedral BNT lattice, the lattice constant increased. A small amount of BCN increased the density and dielectric constant forming the complete solid solution with BNT. However, BCN above 10 mol% was precipitated into a separate phase, and which was detected with XRD. In addition, EDX measurement revealed that Cu in BCN was not distributed homogeneously but was accumulated in a certain area. A lower density with a large amount of BCN was attributed to the nonsinterable property of BCN with large tetragonaliy. The dielectric constant vs the temperature change and the strain vs the electric field indicated that the ferroelectric property of BNT was diminished and paraelectric behavior was enhanced with the BCN addition. BNT-7.5BCN showed a 0.11% unimorph strain with a 9.0 kV/mm electric field with little hysteresis.

The effects of doping on the crystal structure, ferroelectric, and piezoelectric properties of (K,Na) (KNN) ceramics have been investigated. was found to be effective in enhancing the densification and grain growth during sintering. X-ray diffraction analysis indicated that Mn ions substituted B-site Nb ions up to 2 mol%, however, further doping induced unwanted secondary phases. In comparison with undoped KNN ceramics, the well developed microstructure and the substitution to B-sites in 2 mol% Mn-doped KNN ceramics resulted in significant improvements in both piezoelectric coupling coefficient and electromechanical quality factor.